Method for processing light-sensitive silver halide color photographic materials

ABSTRACT

IN THE PROCESSING OF AN EXPOSED SILVER HALIDE COLOR PHOTOGRAPHIC MATERIAL WITH A BLEACH-FIXING SOLUTION CONTAINING A FERRIC SALT OF ETHYLENE DIAMINE TETRAACETIC ACID, QUICK BLEACH-FIXING CAN BE EFFECTED BY INCORPORATING THE BELOW-MENTIONED COMPOUND IN A BATH WHICH IS EMPLOYED PRIOR TO SAID BLEACH-FIXING SOLUTION OF A BLEACH-FIXING BATH.   NH2-C(=S)-NH-(CH2)N-NH-C(=S)-NH2   WHEREIN N IS 0 OR A POSITIVE INTEGER OF 1 TO 5.

"United States Patent 015cc 3,809,563 Patented May 7, 1974 3,809,563METHOD FOR PROCESSING LIGHT-SENSITIVE SILVER HALIDE COLOR PHOTOGRAPHICMATERIALS Takao Nimura and Kunio Jin, Tokyo, and Hajime Komatsu,Odawara, Japan, assignors to Konishiroku Photo Industry Co., Ltd. NoDrawing. Filed Mar. 7, 1972, Ser. No. 232,624 Claims priority,application Japan, Sept. 16, 1970,

45/80,51 Int. Cl. G03c 7/16, 5/32 U.S. CI. 9622 6 Claims ABSTRACT OF THEDISCLOSURE In the processing of an exposed silver halide colorphotographic material with a bleach-fixing solution containing a ferricsalt of ethylene diamine tetraacetic acid, quick bleach-fixing can beeffected by incorporating the below-mentioned compound in a bath whichis employed prior to said bleach-fixing solution of a bleach-fixingbath.

H2N(3-NH( 0 H2) nNHi JNH2 Wherein n is 0 or a positive integer of l to5. i

This invention relates to a method for processing lightsensitive silverhalide color photographic materials, particularly to a process for quickbleaching of developed silver image.

Recently, the demand for quick processing of lightsensitive colorphotographic materials has come to be extremely strong. In order tosatisfy the above demand, there are adopted such means as to unite orpartly omit the steps for color development, stopping, fixing,hardening, cleaning, bleaching, stabilization and the like processing ofcolor photographic materials, or to shorten the processing times in theindividual steps. Among these steps for processing of color photographicmaterials, there is a step for bleaching metallic silver formed by thedevelopment of photographic materials. This bleaching is ordinarilyetfected by use of a bleaching bath containing potassium ferricyanide ora water-soluble ferric salt of ethylenediamine tetraacetic acid (EDTA).

The bleaching bath containing potassium ferricyanide is sufficient inbleaching power, but is undesirably strong in oxidizing power.Accordingly, thiosulfate which is a solvent for silver halide cannot beincorporated into the bath, and thus a fixing bath should necessarily beused separately to bring about a disadvantage particularly in the caseof quick processing.

In case the bleaching bath containing a water-soluble ferric salt ofEDTA is used, thiosulfate can be incorporated into the bath, and thusthe bleaching and fixing of photographic material can be effected in onebath. However, the said bath has such drawback that is is weak inbleaching power and requires a long processing time, and the actualstate is such that in case developed silver formed by use of such ablack-and-white developer as used in the case of reversal colordevelopment, an ordinary EDTA ferric salt bleaching bath cannot be putinto practical use because of its being insutficient in bleaching power.

With an aim to increase the bleaching power, there have been proposedmethods using the bleaching bath incorporated with thiourea or itsderivative or with a S-membered heterocyclic compound having a mercaptogroup. However, the former method is disadvantageous in that when thebleaching solution, even in an extremely small amount, is incorporatedinto a color developer, color fog is formed all over the surface oflight-sensitive color photographic material. On the other hand, thelatter method is insufficient in efiectiveness and cannot accomplish theobject of quick processing.-

Under such circumstances as mentioned above, we have now found that acompound of the general formula Br Br wherein R and R are individually ahydrogen atom, a lower alkyl group, an allyl group (C H or an aminogroup; and nis 0 or a positive integer of l to 5, displays a markedlyexcellent bleach-promoting eflect when incorporated into an EDTA ferricsalt bleach-fixing solution. The compound of the Formula I forms no suchcolor fog as in the case of thiourea, even when incorporated into acolor developer and has a bleach-promoting action equivalent to or morethan that of thiourea, even when used in a slight amount, thereby tomake it possible to shorten the bleaching time to V; or more. Further,it has been recognized that even when the compound of the Formula -I isincorporated into a bath used prior to the bleach-fixing, such as astopping, stop-fixing or intermediate bath, the bleach-fixing iscomplete within an extremely short period of time.

Examples of the compound of the Formula I which is used in the presentinvention are shown below, but compounds usable in the present inventionare not limited to these.

Compound 1 HzN-G S NHNHC S-NH1 Compound 2 H502 /NC 8 NHNHC S-NHz HCompound 3 HaC 0H;

NC SNHNHC SN\ H H Compound 4 H5O:

/NC s NHNHC S-NH: H

Compound 5 H5O: (L5H;

/NC s NHNHC SN\ n H Compound 6 HzN NH; NC s NH(CH2)2NHC S-N Compound 7HzN-C S NH(CH2)2NHO S -NH Compound 8 mN-o sivmcrmmno s-NH,

Compound 9 Hm-o s NH(CH2)NHC s-Nm The amounts of the above-mentionedcompounds to be incorporated into bleaching solutions or into variousprocessing liquids used prior to bleaching are preferably Within therange from 0.02 to 5 g./l. (or maximum soluble amounts thereof). Thesecompounds may be used alone or in the form of a mixture of two or more,or may be used in combination with known bleach-promoting agents.

The present invention is illustrated in detail below with reference toexamples.

EXAMPLE 1 A color photographic paper was exposed, subjected to colordevelopment (20 C., 10 min.), stop-fixing (20 C., 3 min.) andwater-washing (l822 C., 5 min.) and then treated with the following EDTAferric salt bleachfixing solution (20 C.):

Water to make 1.0 liter.

The times required for bleaching in the above case were as set forth inTable 1.

TABLE 1 Compound Thlo--- Additive Blank urea 1 1 4 9 Amount (g./1.) 1.00.02 1.0 0.5 0.5

Time required for bleaching (sec.) 110 60 80 40 45 30 From theseresults, it is understood that the compounds of the Formula I are moreexcellent in bleach-promoting action than thiourea.

'EXAMPLE 2 A reversal color film was subjected to the followingprocessings:

(1) First development: 20-1:02 C. (10 min.) (2) First stopping: 20:!:lC. (3 min.)

(3) Water-washing: 20.-' -2 C. (10 min.)

(4) Color development: 20i0.5 C. (9 min.) (5) Second stopping: 20 :1 C.(3 min.)

(6) Water-washing: 20i2 C. min.)

(7) Bleach-fixing: 20 ;1 C. (5 min.)

(8) Water-washing: 20i2 C. min.)

(9) Drying.

First developer:

N-methyl-p-aminophenol sulfate g 2 Sodium sulfite g 50 Hydroquinone g 6Sodium carbonate (monohydrate) .g 45 Potassium bromide g 1 Potassiumiodide mg 10 Potassium thiocyanate g 1.5 Water to make 1.0 liter.

First stopping solution:

Glacial acetic acid ml 15 Sodium acetate g 10 Water to make 1.0 liter.

Color developer: G. Sodium sulfite 3N-ethyl-N-hydroxyethyl-p-phenylenediamine 5 Potassium bromide 1.5Hydroxylamine sulfate 2.5 Sodium carbonate (monohydrate) 50 Water tomake 1.0 liter.

Second sopping solution:

Glacial acetic acid ml 15 Sodium acetate g 10 (Compound 1) g 1.5 Waterto make 1.0 liter.

Bleach-fixing solution: G. EDTA ferric salt 50 Sodium carbonate(monohydrate) 3 Ammonium thiosulfate 240 Anhydrous sodium sulfite 10Wate 2 m ke l-Q liten In case the Compound 1 had not been incorporatedinto the second stopping solution, the color film was not successfullybleached'even when the bleach-fixing time was prolonged to 20 minutes,whereas in case the Compound 1 had been incorporated into said solution,the film was sufliciently bleached in 5 minutes.

EXAMPLE 3 Example 2 was repeated, except that the second stopping waseffected in the same bath as in the first stopping, and the film waswashed with water and then treated at 20 C. for 2 minutes with a 0.1%aqueous solution of each of the Compounds 1 to 9, followed bybleach-fixing. In every case, the bleaching was complete within 5minutes.

EXAMPLE 4 A color photographic paper using a polyethylene laminate paperas the support was exposed and then subjected to the followingprocessings:

Color development: 35 C. (1 min., 30 sec.) Bleach-fixing: 35 C. (1 min.,30 sec.) Water-washing: 3035 C. (2 min.)

Water to make 1.0 liter.

Bleach-fixing solution:

Same as in Example 2.

In case the Compound 3 had not been incorporated into the developer usedin the above, the photographic paper was insufiiciently bleached and wasturbid in color, whereas in case the Compound 3 had been incorporatedinto the developer, the photographic paper was completely bleached and acolor print could be obtained in such a short time as 5 minutes.

What we claim is:

1. In a method for bleach-fixing an exposed, develop light-sensitivesilver halide photographic material with a water-soluble ferric salt ofethylenediamine tetraacetic acid and a fixing agent, the improvementcomprising the bleach-fixing being carried out in the presence of adithiourea compound by processing the photographic material with ableach-fixing solution or with a bath used prior to the bleach-fixing,the solution or the bath containing therein the dithiourea compound inan amount of from 0.02 g. to 5 g. per liter of bath or solution, thedithiourea compound being represented by the general formula:

wherein n is 0 or a positive integer of 1 to 5.

2. A method according to claim 1 wherein n equals 0. 3. A methodaccording to claim 1 wherein n equals 2. 4. A method according to claim1 wherein n equals 4. 5. A method according to claim 1 wherein n equals5., 6. A solution for bleach-fixing an exposed, developedlight-sensitive silver halide photographic material comprising water, awater-soluble ferric salt of ethylenediamine tetraacetic acid, a fixingagent and a dithiourea compound, the dithiourea Compound having beenincors 5 6 porated in an amount of from 0.02 g. to 5 g. per literFOREIGN PATENTS of solution and being represented by the generalformula: 336,257 3/1959 Switzerland 96 60 BF 5 s Q g RONALD H. SMITH,Primary Examiner wherein n is 0 or a positive integer of 1 to 5. 5KELLEY, Assistant EXaminel' References Cited US. Cl. X.R.

UNITED STATES PATENTS 62 XR 3,189,462 6/1965 Bard et a1. 96-60 R3,617,283 11/1971 Ohi et a1 96,-60 BF 3,706,561 12/1972 Mowrey 96-60 R

